Polymers stabilized with orthohydroxyaryl-s-triazines



United States Patent 11 Claims. (Cl. zoo-45.8

This application is a division of Serial No. 93,349, filed March 6,1961, now U.S. Patent 3,118,887.

This invention relates to the stabilization of polymeric materialsagainst the deteriorating effects of ultraviolet light.

More particularly, this invention relates to the stabilization ofplastic and resinous compositions from ultraviolet light by theincorporation therein of one or more members of a class oftris-aryl-triazines wherein the aryl radicals are carbocyclic groups ofless than three 6-membered rings and at least one of the aryl radicalsis substituted by an hydroxy radical which is ortho to the point ofattachment to the triazine nucleus, all further substituents beingeither hydroxy, alkyl, alkoxy, sulfonic, carboxy, halo, haloalkyl oracylamiuo (wherein the acyl is derived from a carboxylic acid).

A good ultraviolet absorber for use in polymeric materials should absorbthe ultraviolet in sunlight and at the same time be a colorless materialby visual observation. The compound should impart no color to thecomposition, should be sufliciently stable to withstand the conditionsof curing of the polymer, and should absorb ultraviolet lightsufiiciently to protect the composition against yellowing anddecomposition on exposure to ultraviolet light. Furthermore, thecompound must have sufficient solubility in various types of materialsso that it may be easily incorporated into various plastic formulations.This latter property is especially important, since an incompletelydispersed product would give poor protection.

Generally, an effective ultraviolet absorber should have its peakabsorption above a wave length of 320 millimicrons. The absorption peakmay be at a higher wave length, as long as absorption drops offsufficiently as it approaches the visual range so that no color isvisible. In addition, to be effective, it should show a high degree ofabsorbency in the desired wave length range. As a measure of the degreeof absorbency, an absorption index may be used. This is a relationexpressed as a figure to show an index of the degree of absorption peramount I "ice good ultraviolet absorbers. structurally, they may berepresented by the following general Formula I:

wherein X, Y and Z are each aromatic, carbocyclic radicals of less thanthree -membered rings (e.g., phenyl, naphthyl and biphenyl), X beingsubstituted by an hydroxy group ortho to the point of attachment to thetriazine nucleus; and each of R, R R R R R R R and R being eitherhydrogen, hydroxy (preferably in the 2,4 and/or 5 position of thearomatic nucleus), alkyl (e.g., methyl, t-butyl, cyclohexyl, t-octyl,n-octyl and dodecyl), alkoxy (e.g., methoxy, n-butoxy, 2-ethylhexyloxyand n-octyloxy), sulfonic, carboxy, halo (e.g., iodo, brorno, andchloro), haloalkyl (e.g. dichloromethyl and trifluoromethyl) andacylamino (e.g. alkanoylamino such as acetamido; monocyclic carbocyclicaroylamino such as benzamido, and monocyclic carbocyclic aromatic-loweralkyl amido such as phenylacetamido).

A preferred class of triazines within the scope of Formula II is:

wherein Q is hydrogen or alkyl (e.g., methyl, ethyl, propyl, n-butyl,t-butyl, cyclohexyl, n-hexyl, n-octyl and ndodecyl) and R, R R R R R andR are as hereinbefore defined.

A particularly preferred class of ultraviolet absorbers for the purposeof this invention are symmetrical trisorthohydroxyphenyl (or naphthyl)-s-triazines further substituted in the aryl moieties at the 4-position,i.e., meta to the hydroxy group by an hydroxy or alkoxy radical.

The derivatives of Formula -I may be prepared by a number of differentmethods. One convenient method involves the trimerization of either ofan ortho-hydroxy substituted aryl amide or an ortho-hydroxy substitutedaryl nitrile. The trimerization is accomplished by heating either thenitrile or the amide above its melting point, but at a temperature belowdecomposition. Suitable amides for this purpose are substitutedsalicylamides as alkylsalicylamide (e.g. 4-methylsalicylamide);hydroxysalicylamide, alkoxysalicylamides (e.g. 4-octyloxysalicylamide,S-methoxysalicylamide and '4-dodecyloxysalicylamide),sulfo-alkoxysalicylamides (e.g. 5-sulfo-4-octyloxysalicylamide);carboxysalicylamides (e.g. 4-carboxy-S-methylsalicylamide);halosalicylamides (e.g. 4-

chlorosalicylamide and S-iodosalicylarnide); halomethylsalicylamides(e.g. 4-trifluoromethylsalicylamide and dichloromethylsalicylamide); andacylaminosalicylamides (e.g. carboxamidosalicylarnides such as4-acetamidosalicylamide and 4a-phenylacetamidosalicylamide);fl-hydroxy-a-naphthamides and a-llYdl'OXY 3 naphthamides such as2-hydroxy-l-naphthamide, 1-hydroxy-2-naphth amide;3-methyl-2,4-dihydroxy-l-naphthamide; alkoxy-Z- hydroxy-l-naphthamides(eg. 4-butoxy 2 hydroxy-lnaphthamide, 4-octy1oxy-2-hydroxy-1-napthamide,and 4- dodecyloxy-Z-hydroxy-l-naphthamide);sulfo-Z-hydroxyl-naphthamides; carboxy 2 hydroxy l naphtharnides;hal-o-2-hydroxy-l-naphtharnides (e.g., 4-chloro-2-hydroxyl naphthamide);halomethylQ-hydroxy-l-naphthamides; acylamino-Z-hydroxy-l-naphthamide;and 4-phenylsalicylamide. The corresponding nitrile compounds canlikewise be trimerized.

Another method of preparing triazine derivatives within the scope ofFormula I is to react a cyanuric halide, e.g., cyanuric chloride with acarbocyclic aromatic compound of less than three 6- m'embered rings. Thesubstituents on the carbocyclic nucleus should correspond to thosepresent on the triazline compound of Formula I. If an amount at leastequivalent to the number of halogen atoms in the cyanuric halide isused, either in the absence of 'a solvent or in the presence of an inertsolvent, a symmetrical tris-orthohydroxyaryl-triazine is obtained. if,on the other hand, it is desired to obtainasymmetrical-triaryl-triazines, the cy'anuric halide is reacted witheither one or two molecular proportions of the aromatic compound toyield intermediates Which are then treated with one or two molecularproportions of another aromatic compound to yield a second intermediate.This is finally treated with a third aromatic compound to yield acompound Within the scope of Formula I. The condensation reaction withcyanuric chloride is conducted in the presence of acid catalyst such asaluminum chloride. The acid catalyst should be present in an amountgenerally equivalent to the number of halogens being substituted.

For the substitution of the group which corresponds to X in (Formula I,various hydroxyaryl compounds of less than three -rnembered rings can beused. For the substitution of the radicals corresponding to Y and Z in{Formula 'I, aryl compounds, with or Without hydroxy radicals, can beused. In all cases, the final triazine derivatiye should contain atleast one ortho-hydroxyaryl radical.

Triazine derivatives of Formula I are useful to protect plastic andresinous compositions against the deteriorating effect of ultravioletlight. Thus, while showing a high degree oat absorbency in theultraviolet light range, they transmit visible light almost completely.They are, thus, especially useful in providing protection wherediscoloration is an undesirable effect.

Generally, any type of polymeric formulation may thus be protected.Among the tremendous array of suitable synthetic resin carrier materialcapable of forming either rigid plastics or elastomers may be mentionedthe acrylic resin, as exemplified by the polymers of acrylic acid,methacrylic acid, methyl acrylate, acrylamide, N-methyl- .ol'acrylamide,acrylonitrile and copolymers of these with styrene, yinylpyridines,etc.; the linear superpolyamides such as nylon; neoprene; condensates ofaldehydes, especially (formaldehyde, and formaldehyde engenderingsubstances such as paraformaldehyde, and hexarnethylene tetramine withurea, thiou-rea and aminotriazines such as melamine and benzoguana-mine,as Well as their ethers with aliphatic alcohols as exemplified bymethanol and but'anol; modified and unmodified condensates of hydroxybenzenes like phenol, resorcinol, etc., with the aforementionedaldehydes; silicones such as dimethyl and methyl hydrogen polysiloxanes;unsaturated, saturated and modified alkyd resins including thcombinations of unsaturated polyesters with cross-limiting monomers suchas styrenated alkyds; the polyolefins as cEor instance the polymers olfethylene, propylene, isobutylene, etc.; vinyl polymers includingpolyvinyl butyral and other acetals, polyvinyl chloride, polyyinylidenechloride, polyvinyl fluoride, polyvinyl acetate and its hydrolysisproducts, polyvinyl chloride-acetate, styrene and substituted styrene(especially otf ring-substituted styrenes, e.-g., 0-, mand p-methylstyrene) polymers and copolymers with acrylonitrile and other terminalethy'lenic monomers such as butadiene and the like; co polymers ofyinylidene chloride with vinyl chloride; cellulose ethers as exemplifiedby ethyl and methyl cellulose; cellulose esters including the nitrate,acetate, propionate, butyrate, etc.; regenerated cellulose;polycarbonates, fluorocarbon polymers such as poly-tetra cfiuoroethyleneand polytrifiuoroethylene; rubber hydrochloride; chlorinated rubber;elastomers such as polymeric dienes, e.g., polychlorobutadiene,polybutadiene, polyisoprene and copolymers of polybutylene, polyethyleneglycol and polypropylene glycol; epoxy resins, as exemplified 'by thecondensates of epiohlorohydrin with bispherrol, diphenylol propane,etc.; polyoxymelthyleue, polyurethane or isocy-anate resins as well ascopolymers and simple mixtures 01f homoand copolymers of any two or moreof such materials. This list is not meant to be limiting or exhaustivebut merely to illustrate the Wide range of polymeric carriers which maybe employed in the pres ent invention, as the vast majority ortsynthetic resins can be used. Thus, ultraviolet absorbers of thisinvention can be included With especial advantage in polyester resinssuch as are described in U.S. 2,255,313, U.S. 2,443,735, US, 2,443,736,U.S. 2,443,737, U.S. 2,443,738, U.S. 2,443,739, U.S. 2,443,740 and U.S.2,443,741. Such resins are prepared from unsaturated polyester resinsprepared from alpha-beta unsaturated polycarhoxylic acids such asmaleic, tfunraric, itaconic, monochloro maleic ianhydride land the like.These unsaturated acids are usually present in amount approximating atleast 20% by Weight of the total Weight of the polymeric polycarboxylicacids used and preferably in amounts varying between about 25 and 65% byWeight based on the total Weight of the polycarboxylic acid present. Ifit is desired to make use of saturated polycarboxylic acid, that is,those which are free of non-benzenoid unsaturation, they also includesuch acids as plrthalic, maleic, succinic, glutaric, setback: andchlorinated polycanbox-ylic acid such as tetrachloro phthalic acid andthe like, preferably in amounts less than a larger proportion of thetotal amount of polycarboxylic acid present.

These acids are condensed with polyhydric alcohols to form theunsaturated polyesters. Usually it is preferred to use alcohols havingonly two hydroxyl groups although minor amounts of alcohols having threeor more hydroxy groups may be used. As dihydroxy alcohols one can useethylene glycol, diett'hylene glycol, propylene glycol, dipropyleneglycol, butanediol-1,-4, butanediol-1,3, butanediol-JJ, pentanediol-lyZ,pentanediol-l,3, pentanediol-l,4, entanediol-LS, hexahediol-Ld, and thelike. Additionally one can use glycerine, pentaerythritol and the like.lEsterification of the alcohol is carried out until an acid number ofthe mixture has been reduced to not over 55.

These polyester groups very often are modified by incorporation of apolymerizable material having a polym erizable CHFC group. Among thesepolymerizable compounds are styrene, substituted styrene such asalphamethylstyrene, and alphaethylstyrene, a ring substituted styrenesuch as 'alkyl styrenes and the like. There are also used allylcompounds such as diallyl phthalate, allyl alcohol, rnethylallylalcohol, allyl acetate, allyl methacrylate, diallyl carbonate, allyllactate, allyl alpha-hydroxylisobutyrate, allyltrichloroxylene,allylacrylate, dially'l- 'malonate, diallyloxylate, diallylgluconate,diallylme-thylgluconate, and many others of this general description.

The modifying polymerizable material is used in a ratio of from parts to90 parts of polyester up to 60 to 40 parts of ester, preferably 25 to 35parts of modifier is used to 65 to 75 parts of polyester.

The ultraviolet absorbers of this invention may also be included withadvantage in oil modified alkyd resins which are extensively used incoatings and are very well described in US. 2,713,039, US. 2,748,092,and US. 2,851,431, especially those modified by reaction with styrene.These resins are essentially the reaction products of drying oils andphthalic anhydride rwith polyhyd ric alcohols modified by reaction withstyrene. Similarly, other surface coating materials such asnitrocellulose and similar materials can also be used.

The preparation, shaping, curing, extrusion, calendering, casting,molding or other forming of these resins is well understood by thoseskilled in the art and accordingly need not be detailed here. Likewise,the formulation of such resins with various additives includingcatalysts, promoters, plasticizers, fillers, reinforcing agents liketextile glass fibers and fabrics, colorants including pigments and dyes,mold lubricants, flow promoters, inhibitors to promote storage life,thickeners, fire retardant agents and other conventional additives iswell known.

In addition to protecting polymer composition itself, the UV absorberdefined by Formula I when incorporated into colored polymers also iseffective in protecting the dye itself, thus preventing or decreasingfading and color change due to exposure to ultraviolet light.

For the purpose of this invention, the UV absorber of Formula I isincorporated into the polymeric material to be protected in amounts offrom 0.01 to 10%, preferably between 0.1 to 2% by weight of thepolymeric composition. It may be incorporated into such compositions byconventional means such as by milling the material to be protected, withor without, other additives and/or modifiers.

This invention is further illustrated by the following examples, inwhich unless otherwise stated, parts are measured on a weight basis.

EXAMPLE 1 2,4,6-tris(2-hydroxy-4-n-octyloxyphenyl -s-triazine4-octyloxysalicylamide is heated in an open flask at 250 C. for sixhours. The residue is cooled, crystallized from pyridine-water and thenrecrystallized from a benzen'e-heptane mixture. The purified productmelts at about 145-147 C.

Analysis.Calcd 'for C H N O C=73.4; H=8.5; N=5.6. Found: C=73.2; H=8.3;N=5.9.

Incorporation of 0.1 parts of the product of Example 1 in 100 parts ofnitrocellulose protects the latter from the deteriorating eifects ofultraviolet light as compared .to the control sample containing no UVabsorber.

6 EXAMPLE 2 2,4,6-tris (2,4-dihydroxyph enyl -s-triazine parts ofcyanuric chloride, parts of resoroinol, 100 parts of aluminum chlorideand 1500 parts of tetrachloroethane are refluxed, with stirring, underanhydrous conditions for 18 hours. The soltvent is then removed withsteam and the residue extracted with boiling alcohol. The insolubleportion is recrystallized from boiling pyridine to give the desiredproduct.

Analysin-Calcd for C H N O C 622; H=3.7; N=l0.2. Found: C='62.2;I-I=3.7; N: 10.1.

Incorporation of 0.1 parts of the product of Example 2 in 100 parts of apolyacrylonitrile resin sold under the trademark Orlon 42 protects thelatter from the deteriorating eifects of ultraviolet light as comparedto the control sample.

EXAMPLE 3 2,4,6 tris (Z-hyd r0xy-4-pr0p0xy ph enyl s-triazines4-propoxysalicylamide is heated at 265 C. for two hours in an openflask. T=he cooled residue is dissolved in hot benzene and on coolingdeposits golden crystals. A recrystallization from a benzene-heptanemixture gives the desired product melting at 202203 C.

Analysis.Calcd. for (1 11 0 0 67.9; H=6.3; N=7.9. Found: C=68.1; H=6.2;N=7.8.

The same product was also obtained by refluxing 10 parts of2,4,6-tris(2,4-dihydroxyphenyl)-s-triazine and 10 parts of propylbromide in 200 parts of 50% aqueous alcohol containing 5 parts of sodiumcarbonate for 20 hours. The cooled reaction mixture was filtered and thesolid collected was triturated with boiling alcohol. The insolubleportion was recrystallized from benzene to yield the desired product.

Replacing propyl bromide with methyl bromide, ethyl bromide, butylbromide, octyl bromide, dodecyl bromide, 2-ethylhexy1 bromide, isooctylbromide, tetradecyl bromide, octadecyl bromide in the procedure ofExample 3, yields the corresponding 4-alkoxy derivatives.

The products thus prepared, when incorporated in polyvinylchloride-vinylidene chloride resins, protect them from deterioratingeffects of ultraviolet light.

EXAMPLE 4 2,4,6-tris-(2-hydr0xy-5-methylphenyl)-s-triazine 23.9 parts ofcyanuric chloride, 50 parts of p-methylanisole, 55 parts of aluminumchloride and 250 ml. of monochlorobenzene (MCB), under anhydrousconditions,

are stirred at room temperature for 16 hours and then heated at 80 C.for 6 hours. The reaction is then treated with dilute HCl and thesolvent removed with steam. The residue is extracted with 250 ml. of MCBand the dried organic solution refluxed with 55 parts of aluminumchloride for six hours. Dilute HCl is then added to the cooled reactionmixture and the solvent removed with steam. The solid residue is thentriturated with hot ethanol and the insoluble residue recrystallizedfrom boiling toluene with activated carbon yielding the product whichmelts at about 276-278" C.

Analysis.Calcd (for C H N O C:72.3; H: .3; N :10.5. Found: C:72.5;H:5.3; N:10.4.

Following the procedure of Example 4 except for the substitution ofequivalent amounts of p-octylanisole for the p-methylanisole usedtherein, there is obtained the product2,4,6-tris-(Z-hydroxy-S-octylphenyl)-s-triazine.

The foregoing products, when incorporated in an amount of 0.2% by Weightinto polyvinyl chloride resins, protect them from deterioration byultraviolet light.

EXAMPLE 5 A. Preparation of 2,4-dichl0r0-6-omethoxyphenyl-s-triazine 110parts of o-rnethoxybenzoguanamide, 6 parts of phosphorous pentachloride,185 ml. of thionyl chloride and 1400 ml. of o-dichlorobe-nzene arerefluxed, with stirring, under anhydrous conditions for 18 hours. Excessthionyl chloride and solvent are removed by distillation under wateraspirator vacuum and the residue recrystallized from 1700 ml. ofmethylcyclohexane and activated charcoal. The crystalline product meltsat about 138- 139 C.

B. 2,4-bis-(2,4-dimethylphenyl)6-ohydroxyphenyl-s-triazine 25.5 parts of2,4-dichloro-6-o-methoxyphenyl-s-triazine, 40 parts of aluminum chlorideand 300 ml. of meta-xylene are refluxed for 18 hours under anhydrousconditions. The reaction mixture is then poured into cold dilute HCl andthe organic layer steam distilled to remove xylene. The residue iscooled and separated by decanting the aqueous layer and then dissolvingit in benzene. The dried benzene solution is then evaporated to drynessand the solid residue is recrystallized from heptane and activatedcharcoal to give the desired product melting at about 130-131 C.

Analysis.Calcd for C H N O: C:78.9 H:6.1; N :11.0. Found: C:79.2; H:6.3;N:11.0.

The products thus prepared when incorporated into a polystyrene resin,protect the latter from the deteriorating effects of ultraviolet light.

In the same manner, the following were prepared.

1 ZA-DIBROMOG- (o-HYDROXY) -s-'IRIAZINE 51 par-ts of2,4-dichloro-6-(o-methoxyphenyl)-s-triazine in 200 partso-dichlorobenzene is treated with anhydrous HBr at 150 C. for 20 hoursand then flushed with dry air and cooled to room temperature. Theprecipitated product is collected and recrystallized frommethylcyclohexane.

2 2-(O-HYDROXYPHENYL)-4,6-BIS-(2,4-DIMETHOXY- PHENYL)-s-TRIAZINE To 10.6parts of 2,4-dibromo-6-(o-hydroxyphenyl)-striazine and 8.5 parts of A101in 150 parts chlorobenzene is slowly added with ice cooling, a solutionof 17.6 parts of dimethoxybenzene in 50 parts chlorobenzene. Thereaction mixture is stirred at room temperature for 16 hours and thenpoured onto an ice-HCl mixture and steam distilled. The aqueous residueis cooled and filtered and the solid product heated with N21 Co inaqueous alcohol. Filtration and recrystallization of the insolubleproduct from methylcyclohexane affords the desired product.

a max.-:85.4 330mg.

(a) 2- (o HYDROX YPHENYL)-4,6-BIS-(2-METHYL-4- METHOXYPHENYL -s-TRIAZINEThis compound is prepared in a manner similar to that described in (2),substituting 15.6 parts of m methylanisole for the dimethoxybenzene:

a max.:64.8 340m EXAMPLE 6 2,4-bis-(2,4-dihydroxyphenyl 6-0-hydronphenyl-s-triazine 25.5 parts of2,4-dichloro-6-o-methoxyphenyl-s-triazine, 40 parts of aluminumchloride, 24.2 parts of resorcinol and 400 parts of tetrachloroethaneare refluxed, with stirring, under anhydrous conditions for 19 hours.The reaction mixture is treated with dilute HCl and steam distilled toremove the organic solvent and the solid residue then extracted with hotethanol. The alcohol insoluble residue is recrystallized from boilingpyridine.

Analysis.Calcd for C H N O 0:648; H:3.9; N :l0.8. Found: C:64.8; H:3.8;N:l0.9.

EXAMPLE 7 2-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)6-(o-hydroxyphenyl) -s-triazine 25.5 parts of2,4-dichloro-6-o-methoxyphenyl-s-triazine, 13.3 parts of aluminumchloride, 11 parts of resorcinol and 300 ml. of monochlorobenzene arestirred under anhydrous conditions for 18 hours at room temperature andthen at C. for 4 hours. The cooled reaction mixture is treated with 13.3parts of aluminum chloride and 200 ml. of meta-xylene and allowed tostir at 90 C. for 8 hours. The solvent is removed with steam and theresidue extracted with boiling ethanol. The alcohol solution isevaporated to dryness and the residue is then recrystallized fromboiling ethanol.

EXAMPLE 8 2,4,6-tris- (Z-hydroxy-I -naphthyl -s-triazine EXAMPLE 9Preparation 0] sulfonic acid derivative of 2,4,6-tris-(o-izydroxyphenyl) -s-triazine 35.7 parts of2,4,6-tris-(o-hydroxyphenyl)-s-triazine are treated with an excess ofconcentrated sulfuric acid at about 75 C. By this reaction, aZ-hydroxy-S-sulfo phenyl derivative is obtained.

EXAMPLE l0 2,4-bis- (2-hydr0xy-5-carboxy phenyl -6- (o-hydroxyphenyl)-s-triazine The procedure of Example 5 Part B is followed except thatthe 300 ml. of xylene is replaced with 28.0 parts of ethylp-methoxybenzoate and 200 ml. of o-dichlorobenzene. The intermediateester is converted to the free acid compound during the steamdistillation to remove the solvents.

EXAMPLE 11 Following the procedure of Example 4 except for thesubstitution of p-methylanisole with 56 parts of p-chloroanisole thereis obtained the product 2,4,6-tris-(2-hydroxy- 5 -chloro -s-triazine 9EXAMPLE 12 2,4,6-trz's-(2,4-dihy'droxy-6-hexylphenyl -s-triazine Asuspension containing 18.4 parts of cyanuric chloride, 58.0 parts of4-hexylresorcinol and 46.5 parts of AlCl in 500 ml. of monochlorobenzeneis cooled until the initial exotherm subsides. It is then heated for 2hours at 75 C. and then at 100 C. for another 2 hours. After cooling,the reaction mixture is poured into an ice-HCl mixture and stirred. Theaqueous portion is decanted and the organic layer steam distilled. Theresidue is filtered and washed with a dilute NaHCO solution and waterand then dried. A benzene solution of the solid is drowned with heptaneand the ensuing product recrystallized from hot glacial acetic acid andnorite. The product does not melt at 360 C.

Analysis.Calcd for C H N O C=70.0; H=7.75; N=6.62. Found: C=69.77;H=7.15; N=6.75.

u-max.=75.7 at 375 m emax.=50,000

EXAMPLE 13 2-(2,4-dihydr0xyphenyl)-4,6-diphenyl-s-triazine Freebenzamidine is prepared from 13.1 parts of its HCl salt and added, as anether solution, to 20 parts of phenyl-B-resorcylate in 50 ml. ofalcohol. The red solution after 18 hours reflux turns yellow and ayellow solid precipitates. The product is filtered and yields 6 g. ofcrude product melting at about 273274 C. Recrystallization from glacialacetic acid yields the pure product melting at about 275-2755 C.

Analysis.Calcd for C H N O C=73.89; H=4.43;

N=12.31; :9.37. Found C=73.44; H=4.49; N =12.17; 0:9.52.

a-max.=52.3 at 344 m eIIl2lX.=17,80O

EXAMPLE l4 20-hydr0xy phenyl-4 ,6 -bis- (4-mezlz0xy phenyl -s-iriazinea-max.=l28.5 at 320 mu, emax.=50,000

EXAMPLE 2,4,6-tris-(2,4-dim th0xyphenyl)-s-triazine and 2,4-bis(2-hydroxy 4-meth0xyphenyl)-6-(2,4-dimeth0xyphenyl)- s-triazine A solutionof 18.4 parts of cyanuric chloride in 100 parts of dimethoxybenzene(DMB) is added over a period of /2 hour to a cold suspension of 39.9parts of AlCl in 100 parts of DMB with vigorous stirring. After 1 hourthe reaction mixture is heated at 75 C. for 14 hours after which it iscooled and poured onto ice HCl and steam distilled. The residue isfiltered and the viscous filtrate made basic with dilute Na CO and thenextracted with hot benzene. Addition of dilute HCl to the benzenesolution precipitates a solid which is collected and tritu rated in hotethanol. The insoluble residue is recrystallized from toluene. andactivated charcoal affording the compound 2,4 -bis( 2hydroxy-4-methoxyphenyl)-6-(2,4- dimethoxyphenyl)-s-triazine, melting at184-185 C.

Analysis.Calcd for C H N O C, 65.10; H, 5.03, N, 9.12; O, 20.75. Found:C, 65.04; H, 5.15; N, 9.24; O, 20.75.

a-max.:97.5 at 333 III/1., emax.=45,000

10 The alcoholic filtrate is cooled to yield 2,4,6-trIs-(2,4-dimethoxyphenyl)-s-triazine, melting at 9495 C.

Analysis.-Calcd for C2'1H27N3O5Z C, 66.24; H, 5.56; N, 8.58; O, 19.61.Found: C, 66.32; H, 5.40; N, 8.88; O, 19.20.

a-max.=86.0 at 313 m emax.=42,000

Controlled dealkylation with HBr of the latter compounds yields2-(4-methoxy-2-hydroxphenyl)-4,6-(2,4-dimethoxyphenyl) -s-triazine.

EXAMPLE 16 2,4-bis-(2,4-dihydr0xyphenyl) -6-(4-meth0xyphenyl) s-triazineAn ether solution containing 42.4 parts of p-methoxyphenylmagnesiumbromide is added slowly, with cooling, to a solution of 23.0 parts ofcyanuric chloride in 200 parts of benzene and the. mixture stirredovernight. The solvent is removed and the solid residue extracted withhot chloroben'zene. This solution is reacted 18 hours at C. with 41parts of resorcinol and 26.6 parts of AlCl The suspension is filteredand poured onto an ice-HCl mixture and heated to 80 C. and filtered hot.The yellow solid is dissolved in hot pyridine and cooled. The first cropof crystals is removed and the filtrate drowned with Water toprecipitate the desired product which is recrystallized from pyridineand found to melt over 360 C.

Analysis.Calcd for C H N O C=65.6; H=4.25; N=10.4. Found: C=65.15;H=4.56; N=10.21.

a-max.=103.'4 at 360 mu, emax.:41,500

EXAMPLE 17 The following mixture is prepared:

Parts Polyvinyl chloride polymer Dioctyl phthalate 45 Dioctyl adipate 15Epoxidized soybean oil 5 Alkylated aryl phosphites 1 Stearic acid 0.252,4,6-tris- (2-hydroxyphenyl -s-triazine 0.1

The ingredients are placed in a jar mill and rolled for six hours, afterwhich themixture is coated on a chrome sheet (15 mil. thickness) andthen oven-curedat 166 F. for three minutes. A portion which is tested onthe Fade- Ometer lasts 2200 hours before appearance of the first spotand 2740 hours before the tenth spot. A control sample without anyabsorber is also tested on the Fade- Ometer. It shows the first spot in1380 hours and the tenth spot in only 1580 hours.

EXAMPLE 18 A mixture of the following is prepared:

Parts Polyvinyl chloride 100 Dioctyl phthalate 45 Epoxidized soybean oil5 Barium-cadmium phenolate 2 Alkylated aryl phosphite 1 'Stearic acid0.5 2,4,6-tris-(Z-hydroxyphenyl)-s-triazine 0.1

11 EXAMPLE 19 Protection of dyed polystyrene against ultraviolet light Anumber of oil soluble dyes as such and containing 0.1% tris-(2hydroxy-4-octyloxyphenyl)-s-triazine as a UV absorber were milled intogeneral purpose polystyrene and the plastic was then exposed in aFade-Ometer for 160 hours. During exposure at 20, 40, 80 and 160 hourintervals, the degree of change in color was measured using acolormaster (results expressed in NBS units, National Bureau ofStandard).

COLOR CHANGE (NBS UNITS) 1 CI is abbreviation for Color Index.

EXAMPLE 20 Z-(Z-hydroxyphenyl) 4,6 (2,4 dimethylphenyD-striazine (2%)was incorporated into polystyrene by milling and a Ma" sheet was molded.The sample, along with the control, was exposed in a Fade-Ometer (POM)and Yellow Index was determined to be as follows:

Yellow Index (Hours in FOM) Contr 6. 5 15. 7 20. 4 28. 82(2-hydroxyphenyl)-4,6-(2,4-dimethylphenyl) -s-triazine 5. 8 10. 0 12. 0l2. 4 16. 7

We claim:

1. A composition of matter comprising a polymeric material and from 0.01to 10% by weight of an ultraviolet light absorber of the formula:

wherein X, Y and Z are each aromatic carbocyclic radicals of less thanthree 6-membered rings, X being substituted by an hydroxy group ortho tothe point of attachment to the triazine ring; and each of R, R R R R R RF and R is individually selected from the group consisting of hydrogen,hydroxy, alkyl, alkoxy, sulfo, carboxy, halo, haloalkyl, alkanoylamino,aroylamino and aralkanoylamino, any alkyl moieties in said substituentsbeing limited to no more than eighteen carbon atoms.

2. The composition of claim 1 wherein the polymeric material is a memberselected from the group consisting of vinyl chloride homopolymers andvinyl chloride copolymers.

3. The composition of claim 1 wherein the polymeric material is apolyolefin.

4. The composition of claim 1 wherein the polymeric material is a memberselected from the group consisting of polystyrene and copolymersthereof.

5. The composition of claim 1 wherein the polymeric material is apolyester resin.

6. The composition of claim 1 wherein the polymeric material is acellulosic resin.

7. The composition of claim 1 wherein the polymeric material is an alkydresin.

8. The composition of claim 1 wherein the ultraviolet absorber is2,4,6-tris(2-hydroxy 4 propoxyphenyl)-striazine.

9. The composition of claim 1 wherein the ultraviolet light absorber is2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- s-triazine.

10. The composition of claim 1 wherein the ultraviolet light absorber is2,4-bis(2,4-dimethylphenyl)-6-(2 hydroxy-4-octyloxyphenyl)-s-triazine.

11. A composition of matter comprising (1) a member of the groupconsisting, of thermoplastic and thermosetting resins and (2) from 0.01to 10% by weight of an ultraviolet light absorber comprising a2,4,6-tris(2-hy droxy-4-alkoxyphenyl)-s-triazine wherein the alkoxyradical has from one to eighteen carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 1,549,901 4/1925Bonhote 260-153 1,566,742 12/ 1925 Fritzsche et al 260248 3,113,940 12/1963 Johns et al. 26045.8 3,113,941 12/1963 Johns et al. 26045.83,113,942 12/1963 Johns et al. 26045.8 3,113,943 12/1963 Johns et al.26045.8 3,134,749 5/1964 Costello et al. 260-4595 OTHER REFERENCES MarkStabilizers, Argus Chemical Corp, 633 Court Street, Brooklyn 31, NewYork, Technical Bulletin No. 1, June 1961. (Copy available in Group140.) Pp. 1, 2, 3, 7 and 9 relied on.

LEON I. BERCOVITZ, Primary Examiner.

F. MCKELVEY, Assistant Examiner.

1. A COMPOSITION OF MATTER COMPRISING A POLYMERIC MATERIAL AND FROM 0.01TO 10% BY WEIGHT OF AN ULTRAVIOLTE LIGHT BSORBER OF THE FORMULA: